Water insoluble carboxylic acid soap-heavy metal salt of hydroxy quinoline fungicidal composition and preparation thereof



FIFSEOi Ilhll bylinfatenteci July 24, 1951 {UNITED} STATE WATER I NSOLUBLE CARBOXYLIC ACID j SOAP-HEAVY METAL SALT OF HYDROXY QUINOLINE FUNGICIDAL COMPOSITION ANDPREPARATION THEREOF Victor N.Kalberg, Chicago, 111., assignor to Scientific OilCompounding Company, Inc., a corporation of Illinois :zLTIhis invention relates to fungicidal and fungistatic compositions and to methods of making the same. In particularit relates to methods of preparing compounds from the water-insoluble metal salts of the hydroxyquinolines, particu larly the, alkalineearth metalsalts, aluminum salt, and heavy metal salts of B-hydroxyquinoline, which compounds are capable of being dissolved or dispersed readily in suitable solvents or vehicles to form jcommercially usable solutions or dispersions which have particular usefulness as fungicidal and/or fungistatic sprays, impregnants endcoa inss- -The compounds of the present invention are thepproducts, of reaction under the influenceof heat. of a waterinsoluble soap, particularly I a water-insoluble soap of an alkaline earth metal or a heavy metal; or aluminum and a waterinsoluble salt, of an ,hydroxy-quinoline, particularly an alkaline earth metal salt orheavy metal salt or aluminum salt of an hydroxyquinoline and particularly an hydroxyquinoline having the ph l c y o y ro oc i a y o ion inthe benzene nucleus ofthe quinoline radical, .3. 1; m r thanonfi s c R iQn-.,, Ex mp es, of these salts are the calcium, barium, magnesium, stro t u d. me cur ma e, ob nickel, iron, copper, cadmium, silver, thallium, tin, zinc and aluminum salts of 5 -hydroxyquinoline,--=.G-hydroxyquinoline, 'Z-hydroxyquinoline or ii-h-ydroxyquinoline. The preferred compounds of: the present invention are the products formed by reacting a heavy; metal soap, particularly ,a copper, zinc or nickel soap, with a heavy metal salt oi B-hydroxyquinoline, particularly thecopper, zinc or nickel salt of 8-hydroxyquinoline.

Of the above named, preferred ,compounds, tiwseior dh reacting a w zi co li soap with the copper salt of S-hydroxyquinoline are the mostdesired-because of their vastly superior fungicidal and/ or fungistatic properties-in which respects they are exceptional. The invention will, therefore, bedescribed with. particular emphasis on these compounds. Copper-8-quinolinolate, the copper salt of 8-, hydroxyquinoline, is a known fungicidal material andis particularly effectiveas a fungicide and as a mildew-proofing agentfor Wood, leathencot-w ton,;wool and other fabric materials made from organic; fibers, protective ccatingsmderivedwfrom No Drawing. Application April s, 1948,

Serial No. 19,432

35 Claims. (01. 260 270) resins, eithernatural or synthetic, Paints, varnishes, and the like. Notwithstanding the efiectiveness of copper-il-quinolinolate as a fungicide its use forthat purpose has been extremely limited in the past due. to its insolubility in water and particularly due to its insolubility in oils, oily materials, benzo toluol, petroleum thinners or mineral spirits andlike organic solvents or thinners commonly used in the coating composition art. j i I vIn accordance 'with the present invention compounds may be made by reacting a water-insoluble soap, especially a zinc, copper or nickel soap, with copper-8-quinolinolate or other alkaline earth metalsalt or heavy metal salt or aluminum salt of an hydroxyquinoline, at an elevated temperature, and these compounds are readily soluble in, or may be dispersed readily in, oils, oily materials, benzol, toluol and the like; and the resulting solutions or dispersions are very effective fungicidal and/or fungistatic compositions. The proportions of the reactants which may be used in preparing this composition may be varied rather'widely, as desired, but it is preferred to use equivalent proportions and from the practical standpoint, at least an equal amount of a water-insoluble soap, with respect to the quinolinolate, on a weight basis, should be used. A substantial excess of metal soap with respect to quinolinolate may be used in carrying out the reaction, without being wasteful of the material, since the proportions of metal soap in excess of that required to react with the quinolinolate serves,,if in suflicient excess, or assists in serving, as a reaction medium in which'the reaction product of the metal soap and the quinolinolate is soluble at elevated temperatures of from about -275 F. and higher, depending upon the particular reaction medium. The reaction temperature may be varied widely, depending upon the particular metal soap used, from about 200 F. to 550 F and higher., 1

The; reaction is carried out in a-reaction medium, preferably in a reaction medium which is capable of withstanding temperatures of about too-550 F. and in which the. reactionproduct is soluble at theelevated temperatures referred to above. This reaction medium may be the same metal soap used in makingthe reaction product as noted above, or it may be some other :metal 3 soap or any mixture of such soaps. It may also be a mixture of a metal soap and a higher fatty acid having at least six carbon atoms in the molecule, such as one of the soap-forming fatty acids named below, or it may be one such higher fatty acid or a mixture of such fatty acids, or it may be a vegetable or animal oil such as linseed oil, China-wood oil, cottonseed oil, soybean oil, palm oil, coconut-oil, sardineor other fish oil, tallow and lard, or the like, or the-mixtures of fatty acids derived from these oils. Preferred reaction media in accordance with the present inventionare oleic acid, noleic acid, caproic acid, caprylic acid, tall oil, palmitic acid, stearic acid, rosin,

abietic acid, and similar soap-forming acids or any combination thereof.

The metal soaps which are used as reactants per-B-quinolinolate went into solution quickly and the resulting solution was a free flowing mass, substantially clear and free from undissolved matter when observed by the naked eye under a light.

The product maintained its liquid state while hot, but at a temperature below about 120 F. it began to solidify and on cooling to room temperature it caked into a relatively soft mass very smooth to the touch when rubbed between the fingers. This solidifiedjprodu ct-was soluble in mineral spirits, vegetable oils, fatty acids, and the like with heating. The temperature at which the mass went into solution in the solvent varied with the particular solvent. Thus, for example,

in accordance with the present invention are water-insoluble soaps of a metal or a mixture ofmetals and a soap-forming acid or a mixture of such acids. Thus, the soaps may besoaps of calcium, barium, magnesium, mercury, lead, cad- With mineral spirits it went into solution at about 175 F., and with linseed oil it went in at about 300 F. The caked solidified product returned to 'the free flowing liquid state on heating to about it-was found that copper-8-quinolinolate readily goes into solution in the zinc oleate solution mium, silver, thallium, manganese, cobalt, nickel,

iron, copper, tin, aluminum and the like. The preferred soaps are thecOpper, zinc and nickel soaps because the results obtained with these soaps are markedly superior to those obtainable with the other soaps referred-to herein.

The soap-forming acids used in forming the aforesaid metal soaps include caproicacid, caprylic acid, capric acid, lauric acid, myristic acid, palmistic acid, stearic acid, oleic acid, linoleic acid, linolenic acid,palmitoleicacid, melissic acid, hydroxystearic acid, ricinoleic acid, and the like, and mixtures thereof. The preferred soapfor-ming fatty acids or materials are those saturated and unsaturated higher aliphatic acids containing from twelve to eighteen carbon atoms, and rosin. Other soap-forming fatty acids which may be, used in forming the 'metal soaps used in accordance with the present invention are the mixed higher fatty acids derived from animal or vegetablesources such as, for example, sardine and other fish oils, lard, coconut oil, sesameoil, soybean oil, tung oil, corn oil or partially or completely hydrogenated derivatives of such oils, fatty acids derived from carnauba, spermaceti, beeswax, candelillafwax and like waxes, and car- 'boxylic acids derived from petroleum or other hydrocarbons. Other soap-forming acids which maybe used are naphthenic acid, tall oil fatty acids, and hydroaromatic acids such as abietic acid and the like. 7

The following example is illustrative of a method of preparing the reactionpr'oducts of the present invention. In this example the heavy metal soap, specifically zinc oleate, is formed in situ, and the reaction medium is ole'i'c acid along with a relatively small proportion of 'zinc oleate in solution in the oleic acid. Also in this example, as well as in all other examples, the term part refers to parts by weight.

EXAMPLE 1 100 parts by weight of oleic acid were heated in an open vessel to a temperature of about 200 'F. and 10 parts of zinc oxide were added and the 7 mixture was heated, with stirring, up to 420 F.

over a period of about 8-10minut'es, at which linolate were stirred into the solution. The icop- 1 when that solution is maintained at temperatures of 300 to 430 F. It was found that at temperatures slightly below abcut 300 F. the copper-8- quinolinolate went into solution very slowly. 'Its "solubility in the zinc oleatesolution at about 300 F. was fairly rapid. The solution of the copper 8-quinolinolate in the zinc'oleate solution at :a temperature of 375-- l.1-0 was prompt.

The novel reaction products of the invention apparently are formed approximately at the time when the quinolinolate dissolves in the reaction medium, for the quinolinolate is insoluble or substantially insoluble in the reaction medium at the reaction temperatures, in the'absence of the metal soap. These reaction products are pref erably not isolated from the reaction medium, for they may be used in accordance with-thepresent invention in the solution or dispersion which results following the reaction, either with or without further solvent or thinner, as fungicidal and/or fungistatic compositions. The proportions of copper-8-quinolinolate used in the above example in making the fungicidal composition'may' be 'varied widely from about 1 part or less up to about 10 /2 to 11 parts; the proportions of the other reactant and the reaction medium remaining constant. With amounts of copper -B-quinolinblate below 10 parts the solutions obtained are improved. In general, the character of the solutions obtained improve progressively Where the amount of copper-'8- quinolinolate used is decreased from the 10 parts in the above example to-about 3 parts. Those obtained with'amounts of copper-8-quinolinolate below about 3 parts do not 'differsubstantially from those obtained using 3 parts. The differences in' solutions referred to are, generally, dif ferences in brilliancy and clarity of solution and in over-all stability as the solution undergoes temperature variations.

The reaction product of a water-insoluble metal soap and'copper-8-quinolinolate or other curator 2 other organic materials'inaccordance with con iventional procedurespf i? j w {:Although the solutions or dispersions of the reaction products'produced in'a'ccordance with Example 1 have'utility 'per se,-their use as such is not desirable because of-the high percentages of copper-S-quinolinolate present in-the compositionin the form of the reaction :product, which is wasteful of the material, and because the hot liquid product, the-solidified'product and the reliquefied product donot have sufficient penetrating properties at normal'room-temper-.- atures-of about TO-75 F. "Accordingly,-the' reaction product of the present" invention may. 'con- 'st'itute a base material which: for commercial purposes may be dis'solved in" or compounded with suitable vehicles: before use, to bring the reaction product to the desired low concentration and to impart to the'product desiredpenetrating and film-forming properties. Thenbase material can be dispersed in water, with the aid of emulsiwfying agents, and it may .betusediin anfaqueous =dispersionif desired: :I l. I

100 parts by weight of oleic acid were heated inan open vessel to'a" temperature of about 200 f. and parts of nickel acetate were added and the mixture was heated, with stirring, up to 420 over a period of about /2 hour, at which time all' of the acetic acidwhich was formed was ,driven off and the nickel oleate which was formed "wentinto solution in'thefexcess of oleic acid. This solution was cooled to about 200 F. and 10 parts of copper-S-quinolinolate were stirred into the solution and the solution was brought up to about 300 F., at which time the copper-S-quinlolinolate went'into solution. The resulting solu-- tion had' greater clarity and brilliancy than the solution of Example, 1. When this solution was cooled to room temperature it thickened some- "what, but retained its liquid state. I This prodnot when thinned withmineral spirits had excellent penetrating properties and functioned eifectiv ely as a fungicidal and-"fungistatic material.

The foregoing example was repeated using,re spectively, equivalent amounts of caproic acid, caprylic acid, lauric acid and tall oil, in lieu of'oleic acid, and the'resulting compounds had both fungistatic and fungicidal efficacy.

In accordance with the present invention I have prepared commercially suitable fungicidal compositions containingthe reaction product of the present invention, which at normal room temperatures are in afree flowing liquid state, i

with the reaction product in uniform solution or dispersion throughout. These compositions remain liquid and constant at temperatures even somewhat below 70 F. Not only do they have particularly effective fungicidal, penetrating and film-forming properties, but, surprisingly, they impart strength tomaterials treated therewith. This will be evident from the test results carried out with the composition produced in accordance withihe following Example 3, which composition ,was identified in these tests as Dri-Seal No. 940.

EXAMPLE 3 "255'1bs. of zinc resinate (8%), 63% lbs. of a -100% phenol-formaldehyde resin of the bis.- phenoltype- [a B.-stage resinhavingan acid number of 83, a melting point (Wilbur method) of 256 F., and a specificgravity-of 20/20 C. of 1.071, and '7 6.5 lbs. of Z-3 (Gardner-Holdt) heat bodied linseed-- oil= were mixed in an open -vessel- -and'the mixturewas heated at about 550 F., withstir-i ring, for one hour. The mass was .then cooled to about"; 300 F. and 43.4 lbs. of copper-8- quinolinolate were added with constant agitation. The temperature was then raised gradually to 400-420" F. at which time the copper-8-quino-, linolate went into solution. Total elapsed time for this stage of the process was onehour. The heat was removed and when the tempera: ture of the solution of the copper-8-quinolinolatezinc resinate reaction product was at about 400 F., 337 lbs. of zinc naphthenate (8%): were added with constant agitation. This effected a temperature drop in the mass to about 275 F. There. was then added to the mass 325 lbs. of 125-127 F. M- P. paraffin'wax and the mixture was stirred until the wax went into solution, At this stage of the process the temperature had droppedto about 200 F. The mass was then thinned with a solution consisting of 4422 lbs. of a solvent of petroleum origin (mineral spirits), 25 /2; lbs. of lead naphthenate (24%) and 74 lbs. o f'cobalt naphthenate (6%).

The petroleum solvent mineral spirits-) -used as a thinner in the above example had an I. B. of 325 and an E. P. of 388, A. P. I." gravity at F. of 45.5, a. sp. gr. at the same temperature of 0.799, and a flash point (TCC) of 116-'F-. Tolu'ol; xylol, carbon tetrachloride and 5 other petroleum solvents or coal tar solvents may be used in lieu of the thinner in the foregoing ex:

ample.

The composition obtained in accordance with Example 3 was a free-flowingliquid at F. It contained" 2.5% of copper-B-quinolinolate based on thew'eig'ht of the solids (on materials other than the thinner). Tests were carried'out on this material (identified as Dri-Seal N0. 940) to determine the efficacy of the materialjas a fungicide and/or fungis'tat and to determine. its

effect on materials treated therewith. .tests I were as follows:

, Dri sealNo. 940 was applied to wood samples 1" x; 3" and leather squares 2" x 2" by soaking I under vacuum for 20 minutes and dryin for 6 hours. The treated specimens and untreated .control specimenswere placed.v on a sterile 30. C. for 14 days:

Chdetoniium flotsam Penicillium citrinum Aspergillus niger Aspergzllus ferreus .Trz'choderma viride Aspergillus flaws.

At the conclusion of this test .period;.;it found that fungi were growing. over the. entire surface of the leather and wood control specimens and that no growth existed on the treated wood and leather specimens.

The treated wood and leather specimens were polished witha conventional polishing material and a high polish wasobtained thereon.

I In additional tests, samples of 10 oziduck' were cut into 4" x 6". squares, the duck waswashed insoap suds, rinsed thoroughly and dried- :10

squares were dipped into Dr'i-Seal' No. 940, drained and driedfor 6 hours.-5.of these dried squares were 7 leached for- 24 hours and v the .1. re-.-

ituwm i mainingfi were'unleached. 7 squares of washed stuck: were left untreated as a control.

All or the squares were buried for l4.days in a soil burial: chamber-at 90 with 98% relative humidity after their tensile strengths were taken 'ona 400 lb. vertical Scott tester. After a 14-day exposure period, all specimens were washed thoroughly warm water and dried inan air conditioning chamber for 24 hours. "Tensile strengths were then taken on the same. Scott tester. Th'eresultsxare reco'rdedin the following table 7 Table '1. S.in T. S. lbs. Not inlbs. 25 ig f Buried Buried SS 9404 L..' 310 343.2 12.3 940Leached 353 255. 2.: .15. s Untreated c 301. 2 13. 8 95. i

n The present invention is not to be construed as limited to the details'of Example 3. Thus, for example the phenol-formaldehyde resin may be omitted or it may be replaced by any resin used in varnish making such as rosin, kauri, copal, congal, ester gum, reaction products of rosin, maleic anhydride. and a polyhydric alcohol such as, glycol, glycerin, pentaerythritol, sorbitol, mannitol, as. well as other synthetic resins. The paraffin wax may be omitted or'it may be replaced by any other suitable water-repellent wax, either animal, vegetable, mineral or synthetic, such as beeswax, carnauba wax, 'spermaceti wax, candelilla wax, and the like. The. zinc resinate in the example may be replaced by alkaline earth metal. or other heavy metal soaps and the linseed oil may be replaced by other suitable vehicles, such as those named above- In general, the vehicle may be any vegetable oil, either'drying or semi-drying or nonedrying, including castor oil and dehydrated caster oil or a combination of either one or .both of these oils with one or more o'ffithe vegetable oils named above. It is, of course, manifest that the alkaline earth metal and heavy metal soap may be formed in situ, as in Example 1. I

' The zinc naphthenate used in preparing the composition of Example 3 functions primarily as a stabilizing material to hold the various solid materials in solution in the thinner and to accelerate drying of the composition. It also functions as an anti-oxidant. Zinc naphthenate can be replaced by small amounts of other suitable anti-oxidants such as phenyl salicylate (in amounts up to about 3%), or by tertiary butyl catechol, hydroquinone and guaiacol (in amounts up to about to 1%). It is preferredfto'use the relatively larger amounts of the' zinc naphthenate of the example, however, because. of its stabilizing and drying properties. The lead naphthenate and cobalt naphthenate serve as. driers and may, of course, be replaced by other suitable driers. Where 'phenyl salicylate is used in the composition, it is found that the stability to light of textiles impregnated with it is improved.

In Example 3, the copper-S-quinolinolate may be varied from about 1 to 3 /2.% by weight, based on the weight of all the constituents-of the composition other than the thinner. The amount of zinc resinate used may also be varied, up or down about 25% from the amount stated. The linseed oil may be varied up or down 25% from the amount. statedand the zinc naphthenate can be variedc50.%. up or down from the amount stated.

8 latter-can, of coursabeomitted, .asfianalso the resin and wax, as noted above. Ifit, desired to enhance the water-proofing properties of the composition the amount of wax used may be increased up to 100% of that stated. Other var,- iatio'ns will readily suggest themselves to a skilled workerin the art.

Additional reaction products in accordance with the present invention were prepared as:-de scribed in the following Examples 4 to 14 and tested to determine the emcacy thereofas fungi.- stats... ISolutions ofseach of these products were used to impregnate leather specimens and these specimens were placed, along with a control spec,- imen, in petri dishes containing a substratum consisting of a sterile nutrient agar medium having a pH of 5.5. The specimens were sprayed with a spore, suspension similar to. thatdcscribed above'and incubated at 30 C. for d days. Fungi were growing over the entire surfa-ce of the controlv specimen at the conclusion of the test period,'whereas the treated specimens were substantially free of such growth. Some ofathe treated specimens had no fungus growth thereon, as observed with the naked eye, even on the 14th day.

The specimen treated'wit'h the reaction product of nickel caproateand 'copper-B-quinolinolate, prepared in accordance with Examplel-3, was remarkably clean of fungus growth. on the 16th day. It was observed during the test period that there was a clean field of substratum surrounding this specimen, thereby indicating that the impregnant was having a lethal effect on the fungi. T

EXAMPLE 4 625 parts of nickel oleate were dissolved in 565 parts of oleic acid. This solution was heated'fto 450 F. and. parts of nickel-8-quinolinolate were added with stirring. The addition is preferably accomplished in increments of 10 to 20 parts, one increment dissolving completely before another is added. The mixture was heated with stirring for about 10 minutes and allowed to cool. The resulting solution was a freelfiowing mass at room temperature. Solutions of this material in benzol, toluol and petroleum thinner (mineral spirits) were perfectly clear and light reen in color.

EXAMPLE 5 625 parts of nickel oleate were dissolved in 565 parts of oleic acid. This solution was heated to about 450 F. and 120 parts of barium-8-quinolinolate were added in increments of 10 to 20 parts. with stirring. Heating was continued forsev- Th material was freely soluble in mineral spirits, benzol and toluol at room temperature.

EXAMPLE 6 625 parts of nickel oleate were-dissolved in 565 parts of oleic acid. This solution was heated to about 450 F. and 120 parts-of manganese 'iiquinolinolate were added in increments of 1 0 to 20 parts, with stirring. Heating was continued for several minutes after solution was complete. The resulting solution was allowed to cool to a slightly viscous oil at room temperature. This composition was very soluble in petroleum spirits,

.toluol and benzol at room temperature.

EXAMPLE '7 h 620 parts o f. cop1 )eroleate were dissolved ass-rest between about 200 F. and the lowest decompositiorr temperature of'the. reactants, a. water-insoluble metal carboxylic acid soap and a heavy metal salt of an hydroxyquinoline. The method of forming a composition matter consisting of reacting at a temperature between about 200 F. and the lowest decomposition temperature of the reactants, a'water-insoluble heavy metal carboxylic'acid soap and a heavy metal saltof an hydroxyquinoline.

4. The method of forming a composition of matter consisting of reacting at a temperature between about 200 F. and the lowest decomposition temperature ofizthe reactants, a, water insoluble metal carboxylic acid soap and a wateri'nsoluble meta1-'8:-quinolino1ate. 1 5. The method of) forming a compositionrof matter consisting of reacting at a temperature between about 200'-F. and the lowest decomposition temperature of the reactants, a Water-insoluble heavy metal carboxylic acid soapand a heavy metal-8-quinolino1ate.

' 6., The method of forming a composition of matter consisting of heating below the lowest decomposition temperature of the reactants, a water-insoluble metal carboxylic acid Soap and a-water-insolu-blemetal salt of an hydroxyquino- "lad-The method of forming a composition of matter consisting of heating at a temperature below the lowest decomposiiton temperature of the reactants, a water-insoluble metal carbonyl-i0 acid soap and-an allralinerearth metal salt of an h'iidroxyquinoline.

,8. .I'he-method of forminga composition of matter consisting of. heating ata temepraturc below the lowest decomposition temperature of the reactants, a. water-insoluble heavy metal carboxylic acid soap and a heavy metal salt of an hydroxyquinoline. v V I I '9. The method of ,forming acomposition of matter consistingof heatingata temperature below the lowest decompositiontemperature of the reactants, a water-insoluble heavy metal carboxylic acid soap and a heavy metal-8-quinolinolate. c

10 As a ,fungistaticand/or ,iungicidal composition; the. product produced by the vmethod of claim 3. I s

11. The method. of vforming a composition of matter consisting of heating below the lowest temperature of the reactants, a Water-insoluble heayymetal car-boxylic acid soap and a heavy metal salt of .an hydroxyquinoline wherein the phenolic. hydroxy group is located in any position in thebenzene nucleus of the quinoline radical.

12. As a fungistatic and/or fungicidal composition, the product produced by the method of claim 11.

13. The method of forming a composition of matter consisting of heating below the lowest do composition temperature of the reactants, a water-insoluble heavy metal carboxylic acid soap and copper-8-quinolinolate. I 14. As a fungistatic and/or fungicidal composition, the product produced by the method of claims 13. 15. a fungistatic and/orfungicidal composition, the product produced by the method of claim 6.

' 16. The method of forming a composition of matter consisting of heating below the'lowest decomposition temperature of the reactants, a water-insoluble metal carboxylic acid soap and awater-insoluble metal salt'of an 'hydroxyquinoi 132 line wherein "the phenolic "hydroxy grou is cated in anyposition {in the "benzene nucleus of the quinol'ine radical. I I I 197i As afungiStaticand/orfungicidal composi tion, "the product produced by the method or Iclaiml6. J" '18. The method of forming :a 'composition o f matter consisting of heating below the lowest decomposition temperature of the-"reactants; "a water-insoluble metalwcarboxylic acid soap and a. water-insoluble metal-8 uinolinolate. 19. As a fungistatic and/or fungicidal composition, the product produced by :the method of claim is. c f a I.

20. The -method of formingpw a composition of matter consisting of heating at a temperature below the lowest decomposition temperature of the reactants, .a zinc, carboxylic acid soap and copper-8-quino1ino1ate.

21. As a fungistati'c:andZbrifungicidal composition the productproduced by the methodof claim 20. a

I .22. The method oil-forming a composition of matter consisting of heating at a temperature below the lowest, decomposition temperature, of the reactants, zinc vol'eate and -copper-8'-quinclinolate. V

23. As a fungistatic and/or fungicidal composition the. product. produced by the method of claim 22. i I I v 24. The method of forming a composition of matter consisting of heating at a temperature belowthe lowest decomposition temperature of the reactants, a nickel carboxylic acid soap and copper-S-quinolinolate; r

25'. As a iungistatic and/or .iungicidal compo; sition the product'produced by the method of claim 12, I Y I 26. The method of forming a composition .of matter consisting of heating at a temperature below the ,lowestldecomposition temperature of the reactants, nickel oleate and copper-B-quino linolate. v

27. As a fungistatic and/or fungicidal composition the product ,produced by the method of claim 26.

2.8. The methoduof forming a composition of matter consisting of heating at a temperature below the lowest decomposition:temperature of the reactants, a copper carboxylic acid soap and copper-B-quinolinolate.

29. As a fungistatic and/or fungicidal composition the product produced by the method of claim 28.

30. The method of forming a composition of matter consisting ofheating, at, .a temperature below the lowest decomposition temperature of the reactants, copperoleate and copper-S-quinolinolate. I I p .31. As a fungistatic and/or fungicidal composition the product produced by the method of claim 30.

32. The method of forming a composition of matter consisting of heating at a temperature below the lowest decomposition temperature: of

the reactants, a copper carboxylic acid soap and zinc-8-quinolinolate.

33..As a fungistatic and/or fungicidalcomposition the product produced by the method of claim 32. a I

34. Themethod of forming a composition of matter consisting of heating at a temperature below the lowest decomposition temperature of the'reactants, magnesium olea'te and copper-8 quino1ino1ate.-'- r BUSES mum Muum 2,561,380 13 14 35. As a. funglstatic and/or fungicidal com- UNITED STATES PATENTS position th product produced by the method of Number Name Date claim 1,424,306 Haskins Aug. 1, 1922 VICTOR N. KAI-BERG. 2,069,247 Hoag Feb. 2, 1937 6 2,387,591 Kolb Oct. 23, 1945 2,457,025 Benignus Dec. 21, 1948 REFERENCES CITED OTHER REFERENCES The following references are of record in the Metallic Soaps (1940), Metasap Co., Inc., Harflle of this paaAzenta: l0 rison, N. J., pp. 1, 3, 4, 6, 11, 15 and 18.

Rigler et a1.: Ind. and Engr. Chem, vol. 33, No. 5, May 1941, pp. 693-694. 

1. THE METHOD OF FORMING A COMPOSITION OF MATTER CONSISTING OF REACTING AT A TEMPERATURE BETWEEN ABOUT 200* F. AND THE LOWEST DECOMPOSITION TEMPERATURE OF THE REACTANTS A WATER-INSOLUBLE METAL CARBOXYLIC ACID SOAP AND A WATERINSOLUBLE METAL SALT OF AN HYDROXYQUINOLINE.
 11. THE METHOD OF FORMING A COMPOSITION OF MATTER CONSISTING OF HEATING BELOW THE LOWEST TEMPERATURE OF THE REACTANTS, A WATER-INSOLUBLE HEAVY METAL CARBOXYLIC ACID SOAP AND A HEAVY METAL SALT OF AN HYDROXYQUINOLINE WHEREIN THE PHENOLIC HYDROXY GROUP IS LOCATED IN ANY POSITION IN THE BENZENE NUCLEUS OF THE QUINOLINE RADICAL.
 16. THE METHOD OF FORMING A COMPOSITION OF MATTER CONSISTING OF HEATING BELOW THE LOWEST DECOMPOSITION TEMPERATURE OF THE REACTANTS, A WATER-INSOLUBLE METAL CARBOXYLIC ACID SOAP AND A WATER-INSOLUBLE METAL SALT OF AN HYDROXYQUINOLINE WHEREIN THE PHENOLIC HYDROXY GROUP IS LOCATED IN ANY POSITION IN THE BENZENE NUCLEUS OF THE QUINOLINE RADICAL. 